CN1027509C - Process for the preparation of thermosetting polymers - Google Patents

Abstract

The present invention relates to a method for the preparation of thermosetting polymers, which comprises, in the presence of a metathesis catalyst system comprising a metathesis catalyst and a cocatalyst, reacting a reaction product A or a mixture of a reaction product A and a norbornene monomer and/or an elastomer , for ring-opening bulk polymerization. The thermoset polymers obtained by this method have excellent processability, high heat distortion temperature, and improved impact strength. Said reaction product A is obtained by heat-treating a mixture of 20-95 mole % dicyclopentadiene and 80-5 mole % vinylaromatic compound and has a viscosity below 200 centipoise at 30°C.

Description

The ring-opening polymerization of norbornene monomers such as dicyclopentadiene (DCPD) or methyltetracyclododecene (MTD) in molds and the addition of elastomers as impact modifiers are well known methods .

For example, in Japanese Patent Publication Sho 58 [1983]-129013, a method for preparing thermosetting DCPD homopolymers by reaction injection molding (RIM) using a metathesis catalyst has been disclosed.

In this case, if the elastomer was added to either or both of the two reaction solutions, it was found that its flexural modulus was somewhat reduced, but its impact strength was increased by a factor of 5-10.

In addition, RIM of cycloalkenes containing norbornene rings such as DCPD and MTD is disclosed in Japanese Patent Publication Sho 59(1984)-51911. Even in this bulk polymerization method, an elastomer is mixed in the monomer reaction solution as an impact modifier.

In these disclosed methods, ring-opened polymers have relatively good performances in various physical properties required by engineering plastics, such as impact strength, high elastic modulus, heat resistance, etc., but as required by data, they are very poor. It is difficult to say that they can meet the needs.

For example, it has been pointed out that the glass transition temperature (Tg) of DCPD homopolymers obtained by these methods is insufficient. As an improvement, it has been proposed to copolymerize comonomers with two or more reactive double bonds such as tetracyclododecadiene, propane tris(5-norbornene-2-carboxylate) trimethyl ester, etc., The number of crosslinks is increased by cleavage during polymerization (see Japanese Patent Laid-Open Sho 61 (1986)-179214), but the comonomers used are not readily available.

Furthermore, U.S. Patent 4,703.098 discloses DCPD and its oligomers, which are obtained by heat treatment of DCPD, from which heat-treated products can be prepared with improved Thermosetting resin with glass transition temperature. However, the heat-treated product is difficult to handle due to undeposited white ultra-fine powder during storage.

For example, if the concentration of trimers or tetramers of cyclopentadiene is high in heat-treated products, part of the trimers or tetramers will form white ultrafine powder and precipitate. When the trimers or tetramers This phenomenon will be particularly serious when the concentration of the body is higher than 15% or the storage temperature is lower than 10°C. Due to the sedimentation phenomenon, the pipes of the reaction equipment will be blocked, and the composition or physical properties of the thermosetting resin will also be changed. In order to prevent this phenomenon, it is necessary to heat the product during storage, stir the storage tank or take other troublesome methods. Furthermore, with the increase of terpolymer or tetramer, although the glass transition temperature increases, the impact resistance will decrease, especially after heat treatment.

The present invention relates to a preparation method of thermosetting resin, which comprises the reaction product obtained by heat treatment of the mixture of dicyclopentadiene and vinyl aromatic compound, or the mixture of the above reaction product and norbornene monomer is subjected to ring opening Ontology aggregation. The thermosetting resins obtained by the method of the present invention have excellent processability, high heat distortion temperature and improved impact strength.

As a result of studies aimed at overcoming the above-mentioned problems, the inventors of the present invention have found that an oily product obtained by heat-treating a mixture of DCPD and a vinyl aromatic compound has high polymerization activity and good processability, and found that the oily product is It is possible to produce a thermosetting resin, which is obtained by polymerization of the oily product itself or together with norbornene monomer, has a higher glass transition temperature and improved impact strength, especially after heat treatment test. The ring-opening polymerization of these materials is preferably carried out in a mold of the desired shape in the presence of a metathesis catalytic system.

The gist of the present invention is a ring-opening thermosetting resin characterized by bulk polymerization of the oily product (A) obtained by heat-treating a mixture of dicyclopentadiene and vinyl aromatic compounds, preferably in a mold in the presence of a metathesis catalyst method of preparation. This oily product can be polymerized in the presence of norbornene monomer.

Furthermore, the present invention is characterized in that the above-mentioned oily product (A) or product (A) A method for preparing a thermosetting resin that is subjected to ring-opening bulk polymerization of a mixture of norbornene monomer (B) and an elastomer (C) in the presence of a metathesis catalyst system.

Each part of the present invention is described in detail below.

Dicyclopentadiene (DCPDs) are selected from DCPD itself and substituted DCPDs containing substituents selected from polar and non-polar groups. There may be one or more non-polar groups on DCPD, they are selected from hydrogen, alkyl groups of 1-20 carbon atoms, aryl or alkaryl groups of 6-14 carbon atoms, containing a total of 1-8 DCPD with two carbon atoms has saturated and unsaturated cyclic hydrocarbon groups formed by two ring carbon atoms. In a preferred embodiment, the non-polar group is selected from hydrogen, an alkyl group of 1-3 carbon atoms, and a cyclic group of 5 carbon atoms containing one unsaturated bond. The polar group is selected from acid anhydride, nitrile, acrylate, methacrylate, acetate, halogen, carboxyl, carbonyl and other compounds, preferably dicyclopentadiene.

If the purity of the starting DCPDs of the present invention is generally higher than 90% by weight, preferably higher than 95% by weight, it need not be purified. As a heat-treated product of the monomer, it has high activity and can make the ring-opened polymer have good physical properties.

Dicyclopentadiene generally contains low-boiling and high-boiling impurities. For example, the former mixture includes C hydrocarbons, copolymers of cyclopropadiene (CPD) and butadiene, isopropylene 1,3-pentadiene and other conjugated dienes (such as vinyl norbornene, isopropylene propyl norbornene and propenyl norbornene); the latter mixtures include CPD trimers and co-dimers of CPD and isopropylene, such as methylbicyclononadiene.

C _4-6 hydrocarbons give poor moldability in reaction injection molding, so they should be removed. However, there is sufficient polymerization activity in the present invention even when the purity of the starting material is lower than 98%.

The dicyclopentadiene that can be used in the present invention includes DCPD, methyl and ethyl substitutions of DCPD, and alkyl substitutions of 1 to 6 carbon atoms. The dicyclopentadiene starting material is an endo isomer, an exo isomer or a mixture thereof. When heated, dicyclopentadiene decomposes into cyclopentadiene or its methyl substitutes.

The vinyl aromatic compound used in the present invention is capable of deering with cyclopentadiene (CPD). Diels-Alder reaction compounds, specific examples of which include styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, p-tert-butylstyrene, halogenated styrene or others Styrene, but also vinylnaphthalene or other vinylnaphthalene compounds. Among these compounds, styrenes are preferred.

The molar ratio of DCPDs to vinylaromatics (DCPD/VA) is 95/5 to 20/80, preferably 80/20 to 25/75, most preferably 70/30 to 30/70.

When the amount of DCPDs is too large, a large amount of cyclopentadiene oligomers are produced, and the waxy product is obtained without the formation of an oily product, which is difficult to handle; in addition, it will also damage the impact strength of the thermosetting resin. On the contrary, if the amount of the vinyl aromatic compound content is too large, a large amount of homopolymer of the vinyl aromatic compound is formed or unreacted vinyl aromatic compound remains, resulting in lowering of the physical properties of the thermosetting resin.

In addition, during heat treatment, it is possible to have benzene, toluene, and xylene in the heat treatment reaction, but there must be a solvent removal step after heat treatment. Therefore, it is best not to use solvents if possible.

The norbornene monomer (B) may be used in the present invention in admixture with the heat-treated product (A) of DCPD and a vinyl aromatic compound, if desired. Suitable norbornene monomers contain at least one, preferably two norbornene groups, including substituted or unsubstituted norbornene, dicyclopentadiene, dihydrodicyclopentadiene, tricyclopentadiene ene, tetracyclopentadiene, tetracyclododecene and other norbornene-type monomers containing at least one norbornene group in their structure.

Specific examples of suitable norbornene-type monomers include tetracyclododecene, ethyltetracyclododecene, methyltetracyclododecene, ethyltetracyclododecene, ethylene Tetracyclododecene, phenyltetracyclododecene, 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethylnorbornene, 5-ethyl-2 -norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, Norbornene, norbornadiene, ethylidene norbornene, vinyl norbornene, and phenylnorbornene.

Among these compounds, tricyclic compounds represented by DCPDs and Tetracyclic compounds such as tetracyclododecene, methyltetracyclododecene, and analogs of these compounds.

The molar ratio of DCPD and norbornene monomers used for the purposes of the present invention may vary from 100/0 to 50/50, preferably from 95/5 to 70/30.

The mixing ratio of the oily product (A) and the norbornene monomer (B) can be appropriately selected as required. Usually, the oily product is 100-5% by weight, preferably 100-10% by weight; component (B) is 0-95% by weight, preferably 0-90%. The aryl tetracyclododecene added in the monomer mixture is preferably greater than 2% (weight), especially greater than 3% (weight); the added aryl norbornene is greater than 5% (weight), preferably is greater than 7% by weight.

If the norbornene monomer used is DCPD, the glass transition temperature of the resulting thermosetting resin will decrease as the content of the oily product (A) in the mixture decreases.

In contrast to DCPD (which cures at about 33°C), its mixture with the heat-treated reaction product is liquid at 10°C and is easy to handle and transport. The mixing of the heat-treated product and the norbornene monomer is easily carried out, and the mixer used is a dynamic mixer, a static mixer, an impact mixer or other mixers.

As for the conditions of heat treatment, it is described here that the mixture of DCPD and vinyl aromatic compound is heated at 110-220°C (preferably 150-200°C) for 0.5-20°C in an inert atmosphere (such as nitrogen). hours (preferably 1-10 hours).

Heat treatment may be batch or continuous. In order to control the polymerization of the vinyl aromatic compound, a method of continuously or intermittently adding the vinyl aromatic compound and a method of adding the vinyl aromatic compound midway into a continuous production process may be used. It is also possible to heat DCPDs to the aforementioned temperature at which they decompose into CPD before feeding them, in which case heat treatment at below 50°C is possible.

The resulting polymer can be heat treated to stabilize its physical properties. This heat treatment can be carried out at high temperature until a substantially constant impact strength is obtained. This heat treatment can be performed at high temperature for tens of hours, for example, at 80° C. for 72 hours.

It is desirable to carry out heat treatment in the presence of antioxidants, and it is better to use phenolic antioxidants, such as 4,4'-dioxydiphenyl, hydroquinone monobenzyl ether, 2,4-dimethyl- 6-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-dipentylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4-methyl-2,6- Di-tert-butylphenol, 4,4′-ethylenebis(6-tert-butyl-o-cresol), butylated hydroxyanisole, phenylene ether condensate, butylated phenol, dialkylphenol Sulfides, high molecular weight polyphenols, bisphenols, etc.

Tert-butylcatechol, hydroquinone, resorcinol, 1,2,3-glucinol and other polyphenols may also be used.

The dosage of antioxidant is generally 10-10,000ppm, preferably 100-3,000ppm, calculated on the basis of DCPDs. It is best to add a free radical inhibitor therein.

Examples of free radical inhibitors are p-benzoquinone, p-quinonedioxime, Carbanoxyl and other quinones, tri-p-nitrophenylmethyl, biphenylm-trinitrophenylphenylhydrazone and other nitro compounds, nitroso phenylene and other nitroso compounds, p-phenylenediamine and other amino compounds, dimethyl dithiocarbamate, phenothiazine and other organosulfur compounds, iodine, sulfur, sodium nitrite, and other organic compounds. The consumption of free radical inhibitor is 100-3,000ppm.

The obtained heat-treated product can be used as a raw material for preparing thermosetting resin by ring-opening polymerization. But it is better to remove cyclopentadiene (CPDs), unreacted vinyl aromatics and other low boiling point substances formed when DCPDs decompose.

The products obtained by the heat treatment of DCPDs and vinyl aromatic compounds are generally colorless, transparent oily substances having a viscosity of less than 200 centipoise (30°C), preferably less than 100 centipoise, especially less than 50 centipoise.

Said product contains unreacted DCPDs, small amounts of unreacted vinylaromatics, cyclopentadiene oligomers, co-dimers of cyclopentadiene and vinylaromatics such as phenylnorbornene , naphthyl norbornene, DCPDs Diels-Alder reaction products and co-dimers such as phenyl tetracyclododecene or naphthyl tetracyclododecene, vinyl Polymers of aromatic compounds, etc.

The heat-treated product of the present invention preferably contains less than 5% by weight of unreacted vinyl aromatic compound, especially less than 2% by weight of unreacted vinyl aromatic compound. If it contains a large amount of vinyl aromatic compounds, the glass transition temperature of the thermosetting resin is not high enough.

The content of arylnorbornene as a copolymer of CPD and vinyl aromatic compound is generally greater than 10% by weight, preferably greater than 20% by weight. The content of aryltetracyclododecene as a trimer with CPD and vinylaromatic compound is generally greater than 3% by weight, preferably greater than 10% by weight.

The total amount of reaction products of CPDs and vinylaromatic compounds such as arylnorbornene or aryltetracyclododecene is greater than 15% by weight, preferably greater than 30% by weight. If the said reaction product is increased, the glass transition temperature of the thermosetting resin is increased and the impact strength is also improved, so a high content is preferred.

The content of oligomers mainly composed of trimers and tetramers of DCPDs is generally less than 40% by weight, preferably less than 25% by weight. If the content of said oligomer is high, the heat-treated product will become white cloudy or waxy, and handling will be difficult. Furthermore, the glass transition temperature of the thermosetting resin will increase with the increase of the oligomer, and on the other hand, its impact strength, especially the impact strength after the heat resistance decay test will be lowered unsatisfactorily.

The total amount of aryl norbornene and aryl tetracyclododecene is preferably greater than the amount of CPD oligomers, preferably greater than 2 times, so that the thermosetting resin can have better physical properties.

The content of vinyl aromatic polymers such as polystyrene is less than 30% by weight, preferably 0.1-15% by weight. Within this range, the polymerization activity will not be impaired, and the resulting thermosetting resin will not be substantially affected. However, if its content is too high, the viscosity of the heat-treated product will be too high to cause handling difficulties, and the glass transition temperature will also be lowered.

Elastomers can also be added in the method according to the invention, the starting point being to improve the impact strength. Available elastomers include natural rubber, polybutadiene, styrene/butadiene copolymer (SBR), polyisoprene, styrene/butadiene/styrene block copolymer (SBS), styrene / Isoprene/styrene block copolymer (SIS), ethylene/propylene/diene terpolymer (EPDM), ethylene/vinyl acetate copolymer (EVA) and their hydrogenated products. The elastomers can be used alone or in binary or multicomponent mixtures thereof.

Generally, the elastomer is predissolved in a reaction solution containing the aforementioned product (A) or a mixture of said product (A) and norbornene monomer (B).

If the viscosity of the monomer-containing reaction solution is relatively low, the elastomer may be dissolved therein to properly adjust the viscosity of the reaction solution.

The amount of the elastomer is usually 0.5-20 parts by weight, preferably 1-15 parts by weight, per 100 parts by weight of the thermosetting resin. If the amount of the elastomer is too low, the imparted impact resistance will be small; if the amount is too high, the viscosity of the reaction solution will become too large to make molding workability poor. Also, if too much elastomer is used, the heat denaturation temperature or flexural modulus of the thermosetting resin will decrease.

The catalyst components of the metathesis catalytic system used in the present invention are any metathesis catalytic systems known as norbornene monomer bulk polymerization catalysts, including the catalyst components described in the following patents: Japanese Patent Publication Sh. 58[1983]-127728, Sho 58[1983]-129013, Sho 59[1984]-51911, Sho 60[1985]-79035, Sho 60[1985]-186511, Sho 61[1986]-126115; U.S. Patent 4,380 , 617, U.S. Patent 4,400,340, U.S. Patent 4,481,344; European Unexamined Patents 142,861 and 181,642. None of this is particularly illustrative material.

Suitable catalysts include halides, oxyhalides, oxides, and organic ammonium salts of tungsten, molybdenum, and tantalum. Specific examples thereof include tungsten hexachloride, tungsten oxytetrachloride, tungsten oxide, tri(dodecyl)ammonium tungstate, tridecylmethylammonium tungstate, tri(tributyl)ammonium tungstate, Octylammonium and other tungsten compounds; molybdenum pentachloride, molybdenum oxychloride, tri(dodecyl)ammonium molybdate, methyltrioctylammonium molybdate and other molybdenum compounds; pentachloride Tantalum and its other tantalum compounds. Among these compounds, compounds which are soluble in oily products or norbornene monomers are preferably used as catalysts. From this point of view, it is preferable to use an organic ammonium salt. If the catalyst is a halide, it can be pretreated with alcohols or phenolic compounds to dissolve it. Combinations of benzonitrile, tetrahydrofuran and other Lewis bases, acetylacetone, alkyl acetoacetates and other chelating agents can prevent prepolymerization if desired.

Activators or cocatalysts for metathesis catalytic systems include, for example, alkylaluminum halides, alkoxyalkylaluminum halides, aryloxyalkylaluminum halides, and organotin compounds. Specific examples of suitable cocatalysts include ethylaluminum dichloride, diethylaluminum monochloride, di(ethylaluminum) trichloride, diethylaluminum iodide, ethylaluminum diiodide, Propylaluminum, propylaluminum diiodide, isobutylaluminum dichloride, ethylaluminum dibromide, di(methylaluminum) trichloride, di(methylaluminum) tribromide, tetrabutyltin and halogenated Reaction products of aluminum alkyls with alcohols.

Of these activators, the alkoxyalkylaluminum or aryloxyalkylaluminum halides can be tailored to have a suitable room temperature pot life. Specific examples of the activator include those compounds in Japanese Patent Laid-Open Sho 59 [1984]-51911 and U.S. Patent 4,426,502. If an alkylaluminum halide is used, it is capable of initiating polymerization immediately when mixed with the catalyst. In this case, the use of activators modified with ethers, esters, ketones, nitriles or alcohols can delay the initiation of polymerization (see Japanese Patent Publication Sho 58[1983]-129013, Sho 61[1986]-210814 and U.S. Patent 4, 400, 340). If these modifiers are not used, equipment and handling considerations will be required so that short pot life activators can be used. Alternatively, instead of using a catalyst or activator, a halogen source such as chloroform, carbon tetrachloride, hexachlorocyclopentadiene, other halogenated hydrocarbons, silicon tetrachloride, magnesium tetrachloride, lead tetrachloride and Other metal halides (such as those disclosed in Japanese Patent Publication Sho 60 [1985]-79035 and U.S. Patent 4,481,344).

The catalyst components mentioned above can be used in 0.05-1 parts by weight, more preferably 0.1-0.7 parts by weight, with 100 parts by weight of the total monomers, namely the oily product (A) and the norbornene monomer (B) (if used Norbornene) is calculated based on the total amount.

The molar ratio of the activator or cocatalyst to the catalyst component is usually 0.1-200, preferably 2-10.

It is best to use both the metathesis catalyst and the activator, dissolving them in the monomer. However, they can also be used in the form of suspensions or by dissolving them in small amounts of solvents.

In the present invention, the thermosetting resin is prepared by the following polymerization method: a monomer and a metathesis catalyst system are preferably placed in a mold of the desired shape, and bulk polymerization is carried out in the mold. The presence of small amounts of inert solvents does not hinder the polymerization.

Usually, the monomer is divided into two parts and placed in separate containers, the metathesis catalyst is added to one container, and the activator is added to the other container to form two parts of stable reaction solution respectively. If an elastomer is used, it can be dissolved in either reaction solution.

The two parts of the reaction solution are mixed, and then poured into a molding mold kept at a high temperature, and ring-opening polymerization can occur to obtain a thermosetting resin.

In the present invention, the two-part reaction solutions may be mixed using impingement mixing equipment commonly referred to as RIM molding equipment. In this case, the container containing the two parts is used as the supply source for the different liquid streams. The two streams are mixed immediately in the mixing head of the RIM machine before being poured into a high temperature mold where bulk polymerization immediately proceeds to produce a thermoset resin.

Although impingement mixing equipment can be used, the invention is not limited to this type of mixing. If the two-part solution has a pot life at room temperature greater than 1 hour after the mixing in the mixer is completed, it can be injected or poured into a preheated mold (such as Japanese Patent Publication Sho 59 [1984]-51911 and U.S. Patent 4,426 , described in 502) or pour it continuously. This type of equipment injects the mixture directly into the mold, and such RIM equipment has the advantage of being able to operate at low temperatures.

Furthermore, the present invention is not limited to the use of two-part solutions, and various modifications are readily apparent to those in the industry, such as placing the monomer and a desired additive in a third container, Used as the third stream.

The mold temperature used is usually greater than 30°C, preferably 40-200°C, especially 50-120°C. Molding is generally 0.1 to 100 kg/cm ² .

The polymerization time can be appropriately selected. Usually, the polymerization time is shorter than 20 minutes, preferably shorter than 5 minutes, but can also be longer than this time.

The reaction solution is generally stored or handled under an inert gas such as nitrogen; however, if the solution is not sensitive to air, it need not be stored or handled under an inert gas. The mold does not need to be sealed with an inert gas.

Mixing different fillers such as foaming agent, flame retardant, antioxidant, pigment, colorant, high molecular weight modifier or various other chemical additives, or using glass fiber, carbon fiber, aramid fiber, glass fiber mat The properties of the thermosetting resin of the present invention can be changed when using or other reinforcing materials.

The additive can be mixed with one part of the reaction solution, can be mixed in both parts of the reaction solution at the same time, or can be placed in the mold cavity.

Examples of fillers or reinforcing agents include ground glass, carbon black, talc, calcium carbonate, mica and other inorganic fillers.

In addition to elastomers used as high-molecular-weight additives, there are also hydrogenated additives for thermally polymerized DCPD resins, which are used by dissolving them in a reaction solution.

The bulk polymer obtained by the method of the present invention is a thermosetting resin, which becomes a hard solid after cooling. Its glass transition temperature (Tg) depends on the monomer composition, but its Tg is higher than that of dicyclopentadiene; its glass transition temperature is generally greater than 120°C, preferably greater than 140°C.

Compared with the conventional method of using cyclopentadiene oligomer as a comonomer, the copolymer of the present invention has much higher impact strength, especially the improvement of impact strength after heat treatment is remarkable.

Examples are described below in order to more specifically explain the present invention.

Example 1

50 parts containing 500ppm 2,6-di-tert-butylphenol (BHT) and 100ppm tert-butyl catechu DCPD with a purity of 98.5% of phenol and 50 parts of styrene with a purity of 99.90% were added to the autoclave. The molar ratio of DCPD to styrene was 44:56. After sparging sufficient nitrogen, the mixture was heated to 170°C and reacted for 4 hours. It was then cooled to 80° C., depressurized to 5 Torr, and 1.9 parts of low boiling point substances were removed from the autoclave. Then it was cooled to room temperature to obtain 98.1 parts of a colorless and transparent oily substance. The oily substance has a viscosity of about 20 centipoise (30°C) and a freezing point below -10°C.

The composition of the oily product is as follows:

Unresponsive DCPD: 14%

Unreacted styrene: 1%

Trimers and tetramers of CPD: 10%

Phenyl norbornene: 43%

Phenyltetracyclododecene: 21%

Polystyrene: 10%

Other high boiling point substances: 1%

This oily product was placed in two containers and in one was added 0.4 parts of diethylaluminum chloride (DEAC), 0.15 parts of n-propanol, 0.36 parts of silicon tetrachloride and 5 parts of styrene/isoprene / Styrenic block polymer Kraton 1170 (Shell Co. product), make solution A.

Add 0.3 parts of tri(tridecyl)ammonium molybdate per 100 parts of oily product in another vessel to make solution B.

Pump solution A and solution B into the mixer with a gear pump so that their volume ratio is 1:1. Then it is quickly poured into a mold with a time of 200mm×200mm×3mm and heated to 70° C., the time of pouring is about 10 seconds, and reacted in the mold for 3 minutes. The operation of this system is carried out under the protection of nitrogen.

The glass transition temperature of the product obtained by this method is 158°C (measured with a differential scanning calorimeter); the DuPont impact value is 600kg/cm (according to the falling weight impact strength test JIS K 7211, the radius is 7.9mm and there is a pointed head The breaking strength presented when the drop hammer falls).

The Dupont impact strength of the polymer after heat treatment at 80°C for 72 hours was 250 kg/cm.

Example 2

Mixtures of the composition shown in Table I were prepared using the heat-treated product of Example 1 and DCPD. Prepare solution A and solution B according to the method of example 1. After molding, a molded product is obtained. The physical properties of the molded products are shown in Table I.

Regarding the freezing point of the mixture, the mixture of the invention does not freeze even at -10°C, in contrast to DCPC which freezes at 33°C.

Table I

Comparative examples of the present invention

Test No. 2-1 2-2 2-3 2-4

DCPD/product mixing ratio 30/70 50/50 70/30 100/0

Glass transition temperature (Tg) 156 154 153 150

DuPont impact value (kg/cm) 600 500 400 200

DuPont impact value (heating at 80°C for 72 hours) 250 170 150 100

(kg/cm)

Example 3

Except that the addition amount of DCPD and styrene raw materials is the amount shown in Table II, the oily product is obtained by the operating method of Example 1. The composition of the obtained oily product, the turbidity of the solution and its freezing point are shown in Table II.

Except for the oily product, molded products were prepared in the same manner as in Example 1, and the physical properties of the obtained molded products are shown in II.

Table II

Comparative example Example of the present invention

Test No. 1 2 3

Raw material addition amount (molar ratio) 100 65 34

Styrene 0 35 66

Composition of reaction products

Unreacted DCPD 40 27 8

Unreacted styrene - 0.4 2

CPD trimers and tetramers 60 18 3

Phenyl norbornene - 29 49

Phenyltetracyclododecene - 17 24

Styrene - 8 14

Other - 0.6 24

reaction product state

white turbid state massive waxy colorless colorless

white precipitate transparent transparent

Freezing point (℃) 50 -10＞ -10＞

RIM molded products

Glass transition temperature (°C) 190 168 150

DuPont impact value (kg/cm) 150 600 ＞700

DuPont impact value (heating at 80°C for 72 hours) 40 220 250

(kg/cm)

Example 4

Using 50 parts of 98.5% pure DCPD and 50 parts of 98.0% pure vinyltoluene containing 100 ppm tert-butylcatechol and 1000 ppm 4,4′-methylenebis(6-tert-butyl-o-cresol) , heat-treated according to the method of Example 1, to obtain a colorless and transparent oily product with a viscosity of 10 centipoise (30°C).

The composition of the oily product is as follows:

Unresponsive DCPD: 8%

Unreacted vinyltoluene: 2%

CPD trimers and tetramers: 15%

Tolyl norbornene: 51%

Tolyl tetracyclododecene: 17%

Polyvinyl toluene and others

High boiling point substances: 7%

A molded product was obtained as in Example 1 except that 30 parts of this oily product and 70 parts of DCPD were used.

The freezing point of the mixture is below -10°C. The glass transition temperature (T) of the resulting molded product was 155°C. The DuPont impact value is 600kg/cm, and the DuPont impact value after heat treatment is 250kg/cm.

Example 5

This example uses continuous feeding technology.

Mix DCPD with a purity of 98.5% and styrene with a purity of 99.9% containing 1000 ppm of 4,4'-methylenebis(2,6-di-tert-butylphenol) in equal parts by weight to obtain a reaction solution , added to a 3-liter reactor with an external heating and cooling device at a feed rate of 1.0 liter per hour through a raw material supply pipe, and maintained a constant temperature of 60°C.

The solution leaving said reactor was introduced into another 3 liter reactor through another product solution outlet pipe. Thereafter, it flows into a flash column operating under a vacuum of 5 torr through a product solution outlet pipe and a constant pressure valve, where low boiling point substances are evaporated at a rate of 0.05 liters/hour, and are liquefied by a condensing heat exchanger, from removed from the system.

The heat-treated product is provided for use through an outlet pipe. The obtained heat-treated product was colorless and transparent. Its composition is as follows:

Unresponsive DCPD: 12%

Unreacted styrene: 2%

CPD trimers and tetramers: 8%

Phenyl norbornene: 51%

Phenyltetracyclododecene: 17%

Polystyrene: 9%

Others: 1%

Molded products were obtained as in Example 1 except that a mixture containing 30 parts of the oily product and 70 parts of DCPD was used.

The freezing point of the mixture is below -10°C, the glass transition temperature of the obtained molded product is 155°C, the Dupont impact value is 500kg/cm, and the Dupont impact value after heat treatment is 200kg/cm.

Example 6

According to the method of example 5, except supplying raw material from raw material supply pipe, in addition the raw material solution that will contain 30 parts of DCPD and 70 parts of styrenes is added reactor from another raw material supply pipe with the speed of 0.3 liters/hour, total supply raw material The molar ratio of DCPD and styrene in is 40:60. The obtained oily product was colorless and transparent. Its composition is as follows: bright shape. Its composition is as follows:

Unresponsive DCPD: 15%

Unreacted styrene: 2%

CPD trimer and tetramer: 5%

Phenyl norbornene: 53%

Phenyltetracyclododecene: 21%

Polystyrene: 3%

Others: 1%

Molded products were obtained as in Example 1 except that a mixture containing 30 parts of the oily product and 70 parts of DCPD was used.

The freezing point of the mixture was lower than -10°C, the obtained molded product had a glass transition temperature of 165°C, a DuPont impact value of 500 kg/cm, and a DuPont impact value of 190 kg/cm after heat treatment.

Example 7

Except that DCPD is additionally supplied through a raw material supply pipe at a rate of 0.3 liters/hour, the reaction is carried out according to the method of Example 5, heated to 180 ° C in a heat exchanger with an internal volume of 0.2 liters, and fed into a reactor as in Example 5 . The molar ratio of DCPD to styrene in the total feed was 56:44.

The obtained oily product is colorless and transparent, and its composition is as follows:

Unresponsive DCPD: 18%

Unreacted styrene: 1%

CPD trimers and tetramers: 8%

Phenyl norbornene: 45%

Phenyltetracyclododecene: 23%

Polystyrene: 3%

Others: 1%

A molded product was obtained as in Example 1 using a mixture containing 20 parts of this oily product and 80 parts of DCPD.

The freezing point of the mixture is below -10°C. The obtained molded product had a glass transition temperature of 170° C., a DuPont impact value of 600 kg/cm, and a DuPont impact value of 220 kg/cm after heat treatment.

According to the present invention, using oily, easy-to-handle monomers obtained from DCPC and vinyl aromatic compounds, heat distortion temperature (glass transition temperature), drop-weight impact strength (especially drop-weight after heat treatment) can be obtained impact strength) better thermosetting resins than conventional DCPD polymers. The thermosetting resin of the present invention has excellent properties so that it can be widely used in various fields requiring heat resistance and impact resistance.

Claims (4)

1, a kind of preparation method of thermosetting polymer, this method comprises, in the presence of the metathesis catalyst system that includes a kind of metathesis catalyst and a kind of promotor, adopt the method for open loop mass polymerization to carry out polymerization to following reaction product, described reaction product is to obtain by the mixture of 20～95 moles of % Dicyclopentadiene (DCPD) and 80-5 mole % vinyl aromatic compounds is heat-treated, and its viscosity in the time of 30 ℃ is lower than 200 lis of dregs of rice.

2, method according to claim 1 wherein, is carried out polymerization with described reaction product with the elastomerics of counting 0.5～20 weight part for base by prepared thermosetting polymer 100 weight parts.

3, a kind of preparation method of thermosetting polymer, this method comprises, include a kind of metathesis catalyst and a kind of promotor metathesis catalyst system in the presence of, adopt the method for open loop mass polymerization to carry out polymerization to said mixture, described mixture forms by following mixed for (A) with (B)

(A) reaction product that obtains through thermal treatment of the mixture of a kind of 20～95 moles of % Dicyclopentadiene (DCPD) and 80-5 mole % vinyl aromatic compounds, its viscosity in the time of 30 ℃ is lower than 200 lis of dregs of rice,

(B) have the norbornene monomer of a norbornene at least,

(A) and amount (B), be base by (A) and gross weight (B), be respectively at least 5 weight % and be not more than 95 weight %.

4, method according to claim 3 wherein, with the mixture of described product (A) with norbornene monomer (B), is carried out polymerization with the elastomerics of counting 0.5～20 weight part for base by prepared thermosetting polymer 100 weight parts.